Haloethersilanes



United States Patent 3,334,123 HALOETHERSILANES Alan L. Culpepper, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Filed Oct. 9, 1963, Ser. No. 314,879 5 Claims. (Cl. 260448.8)

This invention relates to silanes with one haloether substituent, the quaternary ammonium salts of these silanes, and siloxane polymers that can be made from these substances. This invention also relates to the use of these substances as a new form of fabric water-repellent when used per se and when used in conjunction with other silicone water repellents.

The haloethersilanes of this invention are of the formula H i t X 0R-Si1Q I Q]! where Q, Q and Q" can each be hydrogen, halogen, hydroxy, any monovalent hydrocarbon or halohydrocarbon radicals that are free of aliphatic unsaturation, any radical of the formulae KO- ECOO, ll C=N--O- and FC=NO where F is a hydrocarbon or halohydrocarbon radical or radicals of the formula where R" is an alkyl radical of 1 to 4 carbon atoms, and

m is an integer from 1 through 2, R is a divalent aliphatic or cycloaliphatic hydrocarbon radical with more than one carbon atom, R is hydrogen or -a monovalent hydrocarbon radical with 1 through 6 carbon atoms, and X is a halogen atom.

These haloether silanes are prepared in the following manner:

where W is a monovalent unsaturated aliphatic or cycloaliphatic hydrocarbon radical. The reaction proceeds by the addition of a silicon hydride across an unsaturated carbon link, i.e.:

The conditions for carrying out the reaction are the standard conditions for adding SiH to C C.

The appropriate haloether can be prepared for use in the above reaction by the following method:

1] Low temp. WOH ROH HX This is a standard synthesis, being described in Organic Synthesis, vol. 1, second edition, p. 377 (1944).

If any or all of the substituents on the silane represented by Q, Q, and Q" are hydrolyzable groups such as hydrogen, alkoxy, acyloxy, phenoxy, or Ketoxirne, the haloether silanes can then be polymerized to silox-anes by standard hydrolysis methods well-known to the art, or copolymerized with other silanes by the same methods. Since alpha-haloethers are themselves reactive towards water, it is best to employ only that amount of water needed to hydrolyze the silicon-bonded hydrolyzable groups. Alternatively, the haloether silanes can be reacted with a hydroxyl-endblocked preformed copolymer, forming copolymers through an anhydrous reaction.

III

Such haloether siloxane polymers and copolymers are represented by the following: a siloxaue with at least one unit of the Formula 1:

H QLI X ORSiOo-m) where n is an integer of 0 through 2 and the other symbols are as shown above, any other units in the siloxane being of the Formula 2:

where a is an integer of 0 through 3, and Y is hydrogen, any monovalent hydrocarbon or h-alohydrocarbon radical, any radical of the formulae O, COO, R C=NO, =C==NO or RO(CH CH O) as defined supra, or hydroxy radicals. The copolymers of this invention can contain more than one species each of (1 and (2) A quaternary ammonium salt can be made from the haloether silanes of this invention by the following reaction:

Where Z is a tertiary amine containing no more than one aromatic group, and the other symbols are as defined above.

This invention also relates to siloxane polymers or copolymers containing quaternary ammonium salt substituted siloxane units of the formula:

where the symbols are as defined above, any other units in the siloxane being of the formula YBSiO Hi a) where the symbols are as defined above.

These siloxane polymers and copolymers can be prepared by hydrolyzing or cohydrolyzing the corresponding silanes.

The preferred method of making these siloxanes is to react the tertiary amine (Z) with the corresponding haloether siloxane homopolymer or copolymer. When more than one haloether group is present in the original siloxane, more than one quaternary ammonium salt group can be present in the polymer molecule.

The compositions of this invention can be used for rendering substrates water repellent. This utility is exhibited in two Ways. First, the silanes and siloxanes can be used to increase the durability of conventional siloxane water repellents. Second, some of the siloxane copolymers described infra can be used per se as water repellents. In all cases the treatment is particularly applicable to cellulosic fabrics.

It is believed that in both cases the mechanism for improved Water repellency involves a bonding of the quaternary ammonium salt or the haloether group to by droxyl groups on the fabric surface in, for example, the following manner:

Q (fabric)-OH X-ZHilHO REii0a-n r(rest of siloxane) Q'n (fabric) -0 43H 0 RS iO hm-(rest of siloxane) HX-Z As stated above, either silanes or siloxanes can be used. When the hydrolyzable silanes are employed in aqueous medium they will, of course, generate the corresponding siloxane in situ.

When the haloethers are employed one must take care to neutralize the by-produced acid. This can be done by washing the substrate with mild alkali such as alkali metal acetates or ammonium. The purpose of this is to avoid deterioration of the substrate.

When the silanes and siloxanes of this invention are employed to improve the durability of conventional siloxanes, they can be applied to the substrate either before, in conjunction with or subsequent to the conventional siloxane. The precise ratio of the instant compounds relative to the conventional siloxane is not critical although, in general, the haloethers and quaternary ammonium compounds of this invention should constitute less than 50 weight percent of the total organosilicon composition. Preferably, the compositions of this invention are employed in amounts of from 1 to percent based on the weight of the conventional siloxane.

Conventional siloxanes which can be employed along with the compositions of this invention are, for example, aliphatic hydrocarbon and haloaliphatic hydrocarbon substituted siloxanes such as methylhydrogensiloxane, dimethylsiloxane, methylethylsiloxane, methylvinylsiloxane, octadecylmethylsiloxane, and copolymers or mixtures of these and polymers of such siloxanes containing endblocking groups such as trirnethylsiloxane, dimethylhydrogensiloxane and dimethylvinylsiloxane and copolymers containing monoorganosiloxanes such as monomethylsiloxane, monoethylsiloxane and monooctadecylsiloxane. Examples of haloaliphatic siloxanes are heptafluoropentylmethylsiloxane, mono(pentadecylfiuorononyl) siloxane and heptafluoropentylhydrogensiloxane.

It is generally desirable to employ a curing catalyst in conjunction with these conventinal siloxanes such as those commonly employed in curing siloxanes on substrates. Examples of such catalysts are metal salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or zinc octoate or alkanol amine titanates such as triethanol amine titanate.

As stated above, certain copolymers of this invention can be used per se as water repellents. These are copolymers in which the haloethersiloxane and/or quaternary ammonium salt siloxane units composed from .5 to 50 mol percent of the siloxane and the remainder of the copolymer being essentially of units of the formula It is preferred that Y be methyl. The best water repellency is generally attained when the mol percent of the haloether or ammonium salt units in the copolymer is from 1 to 30 mol percent. These copolymers can be applied to the substrate in the form of emulsions or solutions or in any other suitable form.

In both kinds of treatment shown above the amount of siloxane water repellent on the substrate is not critical although, in general, the pick-up runs from 0.1 to 2 percent based on the weight of the substrate. It is desirable that the pick-up should be at least 0.4 percent.

The following is a list of typical species that the various symbols used in this disclosure represent.

Q, Q and Q" can be, among others, any of the following groups: hydrogen, methyl, octadecyl, ethyl, Z-methylpropyl, cyclohexyl, phenyl, B-methylbenzyl, tolyl, 2- phenylpropyl, chloromethyl, trifiuoropropyl, 2,4-dibromocyclohexyl, 2 chlorophenyl, 2-trifluoromethyl-3,3,3-trifiuoropropyl, methoxy, ethoxy, 2chloroethoxy, octadecoxy, cyclohexoxy, 4 chlorocyclohexoxy, 2 methylpropoxy, acetate, propionate, nonadecanoate, isovalerate, cyclohexanecarboxylate, benzoate, crotonate, chloroacetate, 3 trifluoromethyl-4,4,4-trifiuorobutyrate, p-bromobenzoate, 4-chlorocrotonate, phenoxy, chloride, bromide, methylethylisocyanoxy, phenylethylisocyanoxy, cyclohexyl 2-methylvinylisocyanoxy, 4-methylcyc1ohexyl isocyanoxy,

bis-3chloropropyl isocyanoxy, bis-3-chloropropyl isocyanoxy, bis-trifiuoromethyl isocyanoxy, beta-methoxyethoxy, beta-butoxyethoxy, gamma-methoxy-beta-ethoxyethoxy, hydroxy, etc.

R can be any divalent aliphatic or cycloaliphatic hydrocarbon radical of more than one carbon atom such as: ethylene, trimethylene, Z-methyltrimethylene, octadecamethylene, 1,4 cyclohexylene, 1,4 cyclohexenylene-l, butenenylene-l.

R is hydrogen or any monovalent hydrocarbon radical of six carbon atoms or less including methyl, ethyl, 2- methylpropyl, hexyl, cyclohexyl, phenyl, Z-butenyl, etc.

X is a halogen atom, F, Cl, Br. or I.

Y can be, for example, any of the following groups:

hydrogen,

methyl,

octadecyl,

ethyl,

Z-methylpropyl, cyclohexyl,

phenyl,

3-methylbenzyl,

xenyl,

butadienyl, 2-methylpropenyl-2, ethynyl,

cyclohexenyl-2, chloromethyl, trifiuoropropyl, 2,4-dibromocyclohexyl, 2-chlorophenyl, 2-trifluoromethyl-3,3,3-trifiuoropropyl, Z-tribromomethyl, 3,3 dibromopropenyl-2, chloroethynyl, methoxy,

ethoxy,

octadecoxy, cyclohexoxy, 2-methylpropoxy, acetate,

propionate, nonadecanoate, 3-methylbutyrate, cyclohexanecarboxylate, benzoate,

crotonate, chloroacetate, 3-trifluoromethyl-4,4,4-trifluorobutyrate, p-bromobenzoate, 4,4,4-trifiuoro-2,3-chlorocrotonate, phenoxy,

chloride,

bromide, methylethylisocyanoxy, phenylethyl isocyanoxy, 2-methylvinylcyclohexyl isocyanoxy, hydroxy, etc.

Z is any tertiary amine radical containing no more Example 1 Chloromethylallyl ether (ClCH OCH CH=CH was prepared by the method of Shoemaker and Boord [1. Am. Chem. Soc. 53, 1505, (1931)]. In a large separatory funnel suspended in an ice bath was placed 290 g. (5.0 moles) of allyl alcohol and g. (5.0 moles) of p-formaldehyde. Anhydrous hydrochloric acid was added below the surface of the liquid until the solution was clear (about 4 hours). The water layer was removed and the product layer dried. Excess acid was removed by passing dry nitrogen through the solution for one hour. A total of 337 g. (63.5% yield) of chloromethylallyl ether was obtained.

In a one liter flask fitted with a stirrer, condenser, thermometer, and addition funnel was placed 175.2 g. (1.65 moles) of chloromethylallyl ether and 1.5 ml. of 0.1 M chloroplatinic acid in isopropanol. The contens of the flask were heated to 80 C. and maintained at this temperature while 184 g. (1.6 moles) of methyl hydrogen dichlorosilane was added over a period of 6 hours. The product was distilled to yield 229.1 g. (64% yield) of 3-chloromethoxypropyldichloromethylsilane olomoongomoms iom) Example 2 In a 100 cc. flask fitted with a stirrer, condenser, and addition funnel was placed 22.1 g. (0.1 mol) of 3-chloromethoxypropyldichloromethylsilane in 25 ml. of benzene. The flask was cooled with ice and 1.8 g. (0.1 mol) of water was added dropwise. When the addition was complete the solution was stirred for one hour and then dried with Drierite. The solvent was removed under vacuum to give 16.0 g. (96.5%) of a viscous liquid, the siloxane homopolymer of Example 3 When a mixture of 2.5 moles of 3-chloromethoxypropyldichloromethylsilane, 2.5 mols of methyloctadecyldichlorosilane, and 5.0 mols of dimethyldichlorosilane is hydrolyzed (as in Example 2), a viscous copolymer is obtained that consists of 25 mol percent CICHEOCHZCHflCHZSl-O C l s units, 25 mol percent CH3 CrsHa7S iO units and 50 mol percent (CH SiO units.

Example 4 When a mixture of 1.5 mols of S-chloromethoxypropyldichloromethylsilane, 0.5 mol of methyldichlorosilane, and 8 mols of dimethyldichlorosilane is hydrolyzed (as in Example 2), a viscous copolymer is obtained consisting of mol percent CH3 olomoomomornsiio units, 5 mol percent of on. HS lO units and 80 mol percent of (CH SiO units.

Example 5 When a mixture of 1 mol of 3-chloromethoxypropyldichloromethylsilane, 6 mols of methyldichlorosilane, and 3 mols of dimethyldichlorosi-lane is hydrolyzed (as in Example 2), a viscous copolymer is obtained consisting of 60 mol percent of I HSiO 6 units, 30 mol percent of (CH SiO units, and 10 mol percent of OlCHzOCHaCHzCH-zSiO (3H3 units.

Example 6 When 1 mol of 3-chloromethoxypropylidchloromethylsilane is mixed with 1 mol of pyridine, a quaternary ammonium salt is obtained of the following formula:

o1-C omo omomomsron CH3 Example 7 In a 500 cc. flask fitted with a stirrer, condenser, thermometer, and addition funnel was placed 106.5 g. of chloromethyl allyl ether and 0.3 ml. of 0.1 M chloroplatinic acid in isopropanol. The contents of the flask were heated to C. and maintained at this temperature while 135.5 g. of trichlorosilane was added over a period of three hours. The product was distilled through a 24 cm. Vigreaux column to yiled 44.6 g. of 3-chloromethoxypropyltrichlorosilane.

12.1 g. of 3-chloromethoxypropyltrichlorosilane and 20 ml. of ethyl ether was placed in a small separatory funnel, which was then cooled with ice. 1.35 g. of water was added, and the solution was allowed to stand for one hour. The ether was removed by distillation under vacuum to give 5.4 g. of poly(3-chloromethoxypropyl)siloxane.

Example 8 When pyridine is added to 3-chloromethoxytrichlorosilane the pyridinium salt is formed:

Cl- NCHzO CHzOHzCHzSiCls Example 9 A mixture of 0.1 mol of 3-chloromethoxypropylidichlm romethylsilane, 0.375 mol of dimethyldichlorosilane, 0.025 mol of methyltrichlorosilane, and 100 cc. of benzene was rapidly stirred while 9.3 g. of water was added over a period of two hours. Stirring was continued for an additional two hours before excess water was removed by azeotropic distillation. The benzene Was removed under vacuum, and the residue was heated to 80 C. at 2 mm. pressure. A total of 42.3 g. (92% yield) of faintly yellow fluid was obtained which was a copolymer of 20 mol percent 3-chloromethoxypropyl(methyl)siloxane, 75 mol percent dimethylsiloxane and 5 mol percent monomethy1siloxane. Ten g. of this copolymer was dissolved in 13.4 g. of pyridine. A product was obtained that is soluble in water and was a copolymer of 20 mol percent Example 10 Cotton fabric was treated with a solution of a copolymer consisting of percent (CH Si(O) units and 10 percent orns iomomorn o CH2N\ 51- units. The fabric was :then treated with a commercial silicone textile emulsion. Good water-repellent characteristics were exhibited by the fabric.

Example 11 Copolymers consisting of dimethylsiloxane units and CI-OCHzO CHZOHZCEUSIlO units in varying proportions were made by cohydrolysis of the corresponding chlorosilanes by the method of Example 2. Cotton cloth was treated with 2 percent water solutions of these copolymers, dried, and cured for two minutes at 350 F. The durability was determined by washing at 160 F. in a Najort reversing wheel Washer.

Spray ratings after number of 160 F.

M01 percent (OHmSiO in washings co polymer A benzene solution of this copolymer was used to apply the copolymer to the cloth.

Example 12 Cotton print cloth was treated with the following mixtures: 92.725 of Water, 6.6% of a 30% water emulsion of 80% methyl hydrogen siloxane and 20% dimethylsiloxane with OH endblocks, 0.6% of a curing catalyst containing octylene glycol titanate and zinc nitrate, and 0.075% of a copolymer consisting of dimethylsiloxane units and crQEmo omomoms ao units in varying proportions.

The cloth was immersed in the mixture and then run through a paddler to give a wringing action at a uniform pressure, in order to assure a uniform pick-up of siloxane, and then dried. The water repellency is as follows:

Mol percent (CH3)2SiO in copolymer Spray ratingsnumber of 160 F. washings an 100 70 70 6o 90 7O 70 so 90 70 70 on 90 80 80 Control (no copolymer in treating mixture)-.. 100 50 50 Example 13 When the following reactants are reacted in accordance with Example 1, the following products are obtained:

II T 0101110 CEO HSi(O c2115):

l 0101150 omO-suo 01115):

0 ll oiTH-o@or1=om nsuoooirrm omcnona 0-@ ii CITHO CHz-CH2S|1(OC CzHs): oHioHcHa 06 Haloether siloxane copolymers M01 percent Bis(m-to1yl)methylsiloxane 95. 2 E) w (d) BF CH2=CHI?'CHOCH CCH(CHa)aSiO 33.3

Butadienylmethylsiloxane 66. 7

(e) C1-+(GH CHNCHzOCHzOSiOs/n 50.0

(3,3,3-trifiu0ropropy1)p-chlorophenylsiloxane 50. 0

cm (I) Cl-+@NC1H0 CHlCHiSiOa/I 40. o

Example 15 Siloxanes When chloromethoxyallyl ether is added to the following silanes in accordance with the procedure of Example 1, (h/I the following products are obtained. When these silanes 0 (1) 0101110(ofimsuooHzomolh are then partially hydrolyzed by reacting with less than 0 enough water to react with all the silieon-bonded hydrolyzable groups, siloxanes having the following average (2) formulae are obtained. 3113 a ClCHzO(CHz)aSi[O I].1O.o5

l (4) OlCHzO(CH;)3SiOOCCH CH;C1 l

| r"\ (5 C1CH0(CH;)3S1ON:(E 9H,); Silane I Products I n Example 16 When gamma-chloromethoxypropyltrimethoxysilane is CH CH 3 a reacted with benzyldlmethylamlne the silane a HSi(OI)2 momowmnsuoOn: 4 nsitoocornonzoi CICHzO(CH Si[0OCCH2OHzCl] E o1- c: nmomowmnsuoonm is obtained.

1 3 Example 17 When chloromethylallyl ether is reacted with the following silanes, the following haloethers are obtained, which when reacted with pyridine give the following quaternary salts.

Silane Haloether Example 18 To 2000 g. of methylenechloride was added 1022 g. of a dimethylsiloxane polymer With hydroxyl endblocking groups, and 420 g. of

0101-120 CHzCHzOHzSiClz the latter ingredient being added over a period of 20 minutes. The reaction mixture was refluxed until HCl ceased to evolve, the methylene chloride was distilled off, and

the product was vacuum-stripped. The residue was a siloxane copolymer of the dimethylsiloxane and the chloromethylallyl ether silane.

To 500 g. of this residue was added 300 g. of pyridine and 278 g. of water. Then additional water was added to make a 40 percent solution.

4.4 g. of this mixture was mixed with 0.85 g. of sodium acetate and 94.7 g. of water was added.

Cotton cloth was soaked in this latter mixture and then run through a paddler and dried. The ratio of the weight of solid on the cloth to the cloth itself was 1.6 percent.

This cloth was found to have an initial water repellency spray rating of 90 to 100. After one washing the fabric had a spray rating of 90. After three washings the fabric had a spray rating of 80. After five washings the fabric had a spray rating of 80.

That which is claimed is:

1. As a composition of matter, a compound of the formula where Q, Q and Q" are each selected from the group consisting of hydrogen, halogen, hydroxy, monovalent Quaternary Salt E is selected from the group consisting of hydrocarbon and halohydrocarbon radicals,

R" is an alkyl radical of 1 through 4 carbon atoms, and

m is 1 through 2,

R is selected from the group consisting of divalent aliphatic and cycloaliphatic hydrocarbon radicals of more than one carbon atom,

R is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals with 1 through 6 carbon atoms, and

X is a halogen atom.

2. As a composition of matter, a compound of the formula 3. As a composition of matter, a compound of the formula ClCHzO CHzCHzCHzSiCl:

4. As a composition of matter, a compound of the formula 5. As a composition of matter, a compound of the formula C1CH OCH CH CH Si(Cl) References Cited UNITED STATES PATENTS 3,040,080 6/1962 Kopnick et al. 260448.8 3,094,497 6/1963 Hyde 260448.8 3,160,647 12/1964 Chappelow et a1. 260 44815 3,170,894 2/1965 Brown et a1. 26046.5 3,186,963 6/1965 Lewis et a1 26046.5

TOBIAS E. LEVOW, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

M. I. MARQUIS, P. F. SHAVER, Assistant Examiners. 

1. AS A COMPOSITION OF MATTER, A COMPOUND OF THE FORMULA 